NZ200976A

NZ200976A - Haloalkylcarbonylamino-1,3-dioxanes and use as herbicide antidotes

Info

Publication number: NZ200976A
Application number: NZ200976A
Authority: NZ
Inventors: F H Walker
Original assignee: Stauffer Chemical Co
Priority date: 1981-06-16
Filing date: 1982-06-15
Publication date: 1986-02-21
Also published as: CS245772B2; US4561876A; BR8203505A; ES8502984A1; ES513115A0; ATE16285T1; HU191040B; PT75033A; PH17915A; ZA824196B; DE3267138D1; RO87640A2; JPS57212177A; PT75033B; ES8402830A1; AU8491782A; ES524963A0; EP0068709B1; IN155503B; EP0068709A1

Abstract

Certain haloalkylcarbonylamino-1,3-dioxane herbicide antidotes corresponding to the following general formula: <CHEM> wherein R represents chloro-, bromo- or iodo- C1-C4 alkyl; R1 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl or phenyl; R2 represents hydrogen or C1-C4 alkyl; R3 represents hydrogen or C1-C4 alkyl; and R4 represents hydrogen or nitrophenyl; provided that one of R3 and R4 represents hydrogen; are disclosed, as is the production thereof. Such compounds may be formulated with inert diluents or carriers and or adjuvants or with herbicides, in particular thiocarbamates or acetanilides. The use of such compounds counteracts crop damage caused by herbicides and hence provides a method of establishing herbicidal selectivity.

Description

New Zealand Paient Spedficaiion for Paient Number £00976 - • . j; 2 009 7 6 Priority Date(s): J£>.T.^T.

Complete Specification Filed: JvVrft"; Class: Cfi . .O.QJ o w,. • ^ 21 FEB Publication Date: P.O. Journal, No: I $5??.* * ' - / - !$ "l/'V Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION HALOALKYLCARBONYLAMINO-1,3-DIOXANE HERBICIDE ANTIDOTES WE, STAUFFER CHEMICAL COMPANY, a company organised and existing under the laws of the State of Delaware, United States of America, of Westport, Connecticut 06880, United. States of America, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement - 1 -(followed by p*ge I A.) • . A, 2 00974 Field of the Invention This invention relates to herbicide antidotes, and, more particularly, to certain haloalkylcarbonylamino-1,3—dioxanes which are useful as herbicide antidotes. growth, e.g., killing, retarding, defoliating, desiccating, regulating, 10 stunting, tillering, stimulating, and dwarfing. The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, steins, stalks, foliage, and fruits. "Plant growth" includes all phases of development from seed germination to natural or induced cessation of life.

Herbicides are generally used to control or eradicate weed pests. They have gained a higji degree of commercial success because it has been shown that such control can increase crop yield and reduce harvesting costs.' The most popular methods of herbicide application include: 20 pre- plant incorporation into the soil; in-furrow application to seeds and surrounding soli; pre-emergence surface treatment of seeded soil; and post- emergence treatment of the plant and soil.

Background of the Invention An herbicide is a compound which controls or modifies plant A manufacturer of an herbicide generally recommends a range of application rates and concentrations calculated to maximize weed control. The range of rates varies from approximately 0.01 to 50 200976 2 pounds per acre (0.0112 to 56 kilograms per hectare (k/ha)), and is usually in the range of from 0.1 to 25 pounds per acre (0.112 to 28 k/ha). The term "herbicidally effective amount" describes an amount of an herbicide compound which controls or modifies plant growth. The 5 actual amount used depends upon several considerations, including particular weed susceptibility and overall cost limitations.

Hie most Important factor influencing the usefulness of a given herbicide is its selectivity towards crops. In some cases, a beneficial crop is susceptible to the effects of the herbicide. In 10 addition, certain herbicidal compounds are phytotoxic to sane weed species but not to others. lb be effective, an herbicide must cause minimal damage (preferably no damage) to the beneficial crop while maximizing damage to weed species which plague that crop.

To preserve the beneficial aspects of herbicide use and to 15 minimize crop damage, many herbicide antidotes have been prepared.

These antidotes reduce or eliminate damage to the crop without substantially impairing the damaging effect of the herbicide on weed species. See U.S. Patent Nos. 4,021,224 and 4,021,229. ond Belgian Patent Noi 046,094.

The precise mechanism by which an antidote reduces herbicidal crop injury has not been established. An antidote compound may be a remedy, interferent, protectant, or antagonist. As used herein, "antidote" describes a compound which has the effect of establishing herbicide selectivity, i.e., continued herbicidal Cytotoxicity to weed 25 species and reduced or non-phytotoxicity to cultivated crop species. The term "antidotally effective amount" describes an amount of an antidote compound which counteracts a phytotoxic response of a beneficial crop to an herbicide.

Thiocarbamate and acetanilide herbicides are particularly 30 effective in the control of grassy type weeds which interfere with the cultivation of a wide variety of crops, e.g., barley, corn, cotton, lentils, peanuts, peas, potatoes, soybeans, spinach, tobacco ana^tomatoes. Frequently the effective use of these herbicides reqi&reS" / ^ ' addition of an antidote compound. (> 3 200976 Description of the Invention It has now been discovered that certain haloalkylcarbonyl- amino-1,3dioxane compounds are effective antidotes for the protection of a variety of crops from thiocarbamate and acetanilide herbicide injuries. Such compounds have the following formula: in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; R]_ is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group consisting of hydrogen and a nitro group; and either R3 is hydrogen or is hydrogen, provided that when R^, R2 and R4 are all hydrogen and is hydrogen or lower alkyl having 1-4 carbon atons inclusive; then R is other than a l-chloro-2-brcmo-ethyl or l-brano-2-chloro-dthyl radical.

Ihe invention also embodies the above ccnpounds excluding those wherein R4. is a nitrophenyl group.

This invention also embodies a two—part herbicidal system comprised of (a) an herbicidally effective amount of a thiocarbamate com pound of the formula R4 in which R5 is alkyl having 1-6 carbon atoms, inclusive; Rg is selected from the group consisting of alkyl having 1-6 carbon atoms, inclusive; and cyclohexyl; or R5 and R5 form indistinguishable parts of a single alkylene ring having 4-10 carbon atoms, inclusive; and 200976 Ry is selected frcxn the group consisting of alkyl having 1-6 carbon atoms, inclusive; haloalkyl wherein halo is selected from the group consisting of chlorine, bromine and iodine and alkyl has 1-6 carbon atoms, inclusive; alkenyl having 2-6 carbon atoms, inclusive; halo alkenyl wherein halo is selected frcm the group consisting of chlorine, bromine and iodine and alkenyl has 2-6 carbon atons, inclusive; benzyl; and halo-substituted benzyl, wherein halo is selected from the group consisting of 10 chlorine, bromine and iodine; and (b) a non-phytotoxic antidotally effective amount of a compound of the formula ■i^rX R3 \ 0 nR2 Hl| In which R is selected frcxn the group consisting of haloalkyl wherein 15 halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atons, inclusive; Rl is selected frcxn the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atans, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atcxns, inclusive; R3 is selected from the group consisting hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; Ri| is selected from the group consisting of hydrogen and a nitro phenyl group; and either R3 is hydrogen or Rij is hydrogen.

• By way of exemplification, the active thiocarbamate herbicides employed in the invention may include the following: S-ethyl di-propyl thiocarbamate, S-ethyl diisobutyl thiocarbamate, S-propyl di-30 propyl thiocarbamate, S-propyl butylethylthiocarbamate, S-(2,3,3-tri-chloroallyl)diisopropyl thiocarbamate, S-ethyl N-ethyl N-cyclohexyl 7 009 7 thiocarbamate, S-ethyl hexahydro- lH-azepine-l-carbothioate, isopropyl-l-hexahydro-l,4-azepine-l-carbothioate, S-benzyl N,N-disec-butylthiol-carbamate, S-(4-chlorobenzyl) N,N-diethyl thiolcarbamate and combinations thereof.

This invention also embodies a two-part herbicidal system comprised of (a) an herbicidally effective amount of an acetanilide compound of the formula in which rs and r]_q are independently selected from the group consisting of hydrogen; and alkyl having 1-6 carbon atoms, inclusive; and 1-6 carbon atoms, inclusive; alkoxy having 1-8 carbon atoms, inclusive; and carbethoxyalkyl wherein the alkyl group has 1-4 carbon atoms, inclusive; and (b) a non-phytotoxic antidotally effective amount of a compound of the formula in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; R]_ is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atons, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R8 /R9 R9 is selected from the group consisting of alkyl having R4 0 6 R4 is selected from the group consisting of hydrogen and a nitro group; and either R3 is hydrogen or R4 is hydrogen. employed in the invention may include: 2-chloro-2', 6'diethyl-N-(methoxymethyl) acetanilide; 2-chloro-2' -methyl-6' -ethyl-N(methoxy-propyl-(2) )-acetanilide; 2-chloro-2',6'-dimethy 1-^1-(methoxyethyl) acetanilide; 2-chloro-2'-methyl-6'-ethyl-N-(ethoxymethy1) acetanilide; 2-chloro-N-isopropyl acetanilide; 2-chloro-2', 6'-diethyl-N-(n-butoxy-10 methyl) acetanilide; and 2-chloro-N-carbethoxymethy1-26'diethyl acetanilide.

This invention also includes the method of establishing herbicidal selectivity which comprises applying to the locus where protection is desired an antidotally effective amount of a compound of 15 the formula in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; Rl is selected from the group consisting of -hydrogen; lower 20 alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and 25 lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group consisting of hydrogen and a nitro group; and either R3 is hydrogen or R4 is hydrogen.

By way of exemplification, the active acetanilide compounds R4 The locus where selectivity is desired may include soil, 30 seeds, seedlings and vegetation.

' 'A 7 Preparation The thiocarbamates of the present composition are either commercially available or can be prepared by the procedures described in United States Patent Nos. 2,913,327, 2,983,747, 3,133,947, 3,185,720 and 3,198,786. 6 The acetanilides of the present composition are either com mercially available or can be prepared by the procedures described in U.S. Patent Nos. 2,863,752; 3,442,945; 3,780,090; 3,937,730; 3,952,056; and 4,070,179- The haloalkylcarbonylamino-l,3-dioxanes of this invention can 10 be prepared according to the following general procedures, depending upon the starting materials.

In a first procedure, an appropriate haloalkylcarbonyl chlor-' ide is reacted with 5-methyl-5-amino-l,3-dioxane in a basic solution. The reaction is carried out at temperatures below 35°C. The reaction 15 mixture may be stripped and the product recrystallized in ethanol/ water. Structure may be confirmed by nuclear magnetic resonance (MR) spectroscopy.

In an alternate procedure, an appropriate dialkoxy compound is reacted with an appropriate dihydroxyalkyl haloacetamide in an 20 acidic solution. The reaction is.carried out at elevated temperatures. Distillate is collected at 80°C. The distillate may be cooled and washed with sodium carbonate and water. The product may be obtained by removing the solvent in vacuum. Structure may be confirmed by NMR spectroscopy.

The following examples illustrate the preparation of specific compounds.according to these general methods. (Compound numbers correspond to those in Tables I, IV and V). 200976 8 EXAMPLE I (Compound No. l) Preparation of 5-methyl-5-(2',3'-dibromopropionyl) amino-l,3-dioxane Five and nine-tenths grams (g) (0.05 mole) of 5-methyl-5-amino-l,3-dioxane, 3-2 g (0.04 mole) of 50$ sodium hydroxide, 8 milliliters (ml) of water and 55 ml of methylene chloride were combined in a reaction flask. The mixture was cooled to -10°C. Ten g (0.04 mole) of 5 2,3-dibromopropionyl chloride were added dropwise. The reaction mixture was stirred for 2 hours and then vacuum stripped. The product was recrystallized in ethanol/water. Yield was 8.7 g of 5-methyl-5-(2',3'— dibromopropionyl) amino-1,3-dioxane. m.p. = 115-119°C. Structure was confirmed by HMR spectroscopy.

EXAMPLE II (Compound No. 4) Prepration of 5-(2'-bromo-3'-chloropropionyl) amino-5-ej^rl^l>3-dioxane 10 Five and two-tenths g (0.04 mole) of 5-^fehyl-5-amino-l,3-di- oxane, 3-2 g (0.04 mole) of 50$ sodium hydipxlcle, 10 ml of water, and 90 ml of methylene chloride were comljirt^d in a reaction flask. The mixture was cooled to below Eight and two-tenths g (0.04 mole) of 2-bromo-3chloropropic£&7luhloride were added dropwise. The mixture 15 was stirred for l/2"?iour, filtered, dried over magnesium sulfate, and vacuum stripped. Yield was 10.8 g of 5-(21-bromo-3'-chloropropionyl) aminpF^ethyl-l,3-dioxane. m.p. = 95-109°C. Structure was confirmed *tfmx.

EXAMPLE III (Compound No. 10) Preparation of 5-chloroacetylamino-5-ethyl-l,3-dioxane Five and two-tenths g'(0.04 mole) of 5-ethyl-5-amino-l,3-di-20 oxane, 3-2 g (0.04 mole) of 50$ sodium hydroxide, 10 ml of water, and 90 ml of methylene chloride were combined in a reaction flask. The mixture was cooled to below 35 °C. Four and one-half g of chloroacetyl-chloride were added dropri.se. The reaction mixture was stirred for one-half hour, washed with water and dried over magnesium sulfate. The solvent was vacuum stripped. Yield was 5.8 g of 5-chloroacetylamino-5-ethyl-1,3-dioxane. m.p. = 89-95°C. Structure was confirmed by NMR. «j ' »> 9 EXAMPLE IV (Compound No. 18) Preparation of 2-vinyl-5-methyl-5-dichloroacetylamino-l>3-dioxane This example illustrates use of the alternate general procedure.

Six and one-half grams (0.03 mole) of 2,2-(dimethoxyethyl) dichloroacetamide, 3-9 g (0.03 mole) of acrolein diethylacetal, 50 ml of acetonitrile and 0.2 g of ammonium chloride were combined in a reaction flask. The reaction mixture was stirred and refluxed through an attached packed column and variable take-off condenser. Distillate was removed to a head temperature of 78°C.

The reaction mixture was cooled to 40°C and 0.1 g of crushed ammonium chloride was added. The mixture was heated to reflux and distillate was collected between 73 and 81°C. An additional 0.1 g of ammonium chloride was added and the temperature rose to 83°C. Heating was stopped and the hot reaction mixture was poured over ice and extracted twice with 75 ml of dichloromethane. The extracts were combined and washed with 100 ml of water. After drying, the solvent was removed in vacuo to yield 5-0 g of 2-vinyl-5-methyl-5-dichloroacetal-amino-l,3-dioxane, an oil. np30 - 1.498o. Structure was confirmed by MR spectroscopy and gas chromatography.

EXAMPLE V (Compound No. 21) Preparation of 2,2-dimethyl-4-(p-nitrophenyl)-5-dichloro-l,3-dioxane This example demonstrates use of the alternate general procedure.

Six grams (0.019 mole) of chloroamphenicol, 2.3 g (0.022 mole) of-acetone dimethylacetal, 0.2 g of -napthalene sulfonic acid and 60 ml of ethylene dichloride were combined in a reaction flask. The reaction mixture was stirred and refluxed through an attached packed column and variable take-off condenser. Distillate was removed to a head temperature of 80°C. 20097 Ihe distillate was cooled and washed with water, twice with sodium carbonate and a second time with water. The mixture was dried and stripped. Yield was 6.0 g of 2,2-dimethyl-4-(p-nitrophenyl)-5-di-chloro-l,3-dioxane. m.p. = 140-143°C. Structure was confirmed by NMR. i ) < > TABLE i I i Cmpd. No. r Ri CH2-CH H Br Br CH2-CH CH3 Br Br CH2-3- m.p. = 9^-96.5°C dloxane -methyl-5-chloroacetylamino-2,2-di- n^O = 1.4785 methy1-1,3-dioxane 2,2,5-trimethyl-5-dlchloroacetylajnlno- m.p. = 101-104°C 1,3-d loxane 2j2-dlmethyl-5-ethyl-5-chloroacetylamino- m.p. = 67-70°C 1,3-dloxane 2,2-dlmethyl-5-ethyl-5-dichloroacetylamlno- m.p. = 90-93°C 1,3-dioxane 2J5-dlmethyl-2-ethyl-5-chloroacetylamlno- m.p. = 62-69°C 1,3-dioxane 2-allyl-5-methyl-5-chloroacetylamino-l,3- m.p. = 78-83°C . 1,3-dioxane 2-allyl-5-methyl-5-dichloroacetylajnino- n^O = 1.4980 1,3-dloxane 2-phenyl-5-methyl-5-chloroacetylamino-l,3- softened above 95°C dloxane 2-phenyl-5-*nethyl-5-dichloroacetylamino- m.p. = 145-1^8°C 1,3-dloxane 2,2-dimethyl-1I-(p-nltrophenyl)-5-dichloro-m.p. = 1^0-l't3°C acetylamino-1,3-dioxane 2-methyl-4-(p-nitrophenyl )-5-dichloro- glass acetylamino-1,3-dloxane rv> 13 Testing Stock solutions of the herbicides were prepared by diluting the requisite amount of each herbicide in water. Examples of solution compositions and application rates are summarized in Table II.

TABLE II Herbicide Stock Solutions Composition Herbicide Water Application Herbicide Name (mg)* (ml) ml/flat** lb/acre VERNAM® 6E S-propyl N,N- 533 400 5 1.25 dipropyl thio- 3000 500 5 6.00 carbamate EPTAM® 6E 2225 350 5 6.00 S-ethyl N,N-dipropyl thiocarbamate * The weight is measured in terms of mg of formulated herbicide. The formulations used contain about 72% active herbicide compound.

** The flats measure 5-95 inches by 9-5 inches. Approximately four (4) mg/flat is equal to one (1) lb/acre.

The herbicide was either incorporated into the soil prior to 5 planting or applied to the soil after planting and prior to anergence of the plants. In sane cases of pre-plant incorporation, the herbicide was incorporated into the soil alone in preparation for in-furrow application of the antidote; in others the herbicide solution was tank-mixed with the antidote solution prior to incorporation.

Stock solutions of each antidote compound were prepared at the desired concentrations by diluting the requisite amount of each antidote in acetone. Examples of solution compositions, rates and application methods are summarized in Table III.

TABLE III Antidote Stock Solutions Antidote: Haloalkylaarbonylamino-1,3-dioxanes Composition Application Antidote (mg) Acetone (ml) ml/flat lb/acre Method 95 15 1-50 5.00 IF* 60 15 5-00 5-00 PPI** *IF = In-furrow surface application of antidote.

**PPI = Pre-plant incorporation of tank-mixed solution of herbicide and antidote The antidote solutions were applied to the soil either by in-furrow surface application or by pre-plant incorporation. In all cases of pre-plant incorporation, the antidote was tank-mixed with the herbicide prior to incorporation into the soil.

For in-furrow application, a one pint (473 cubic centimeter (cc)) sample of soil containing the previously incorporated herbicide was removed and retained from each planting flat. After leveling and furrowing the soil, seeds of the crop or weed species were planted 1/2 inch deep (1.27 centimeter). Each flat was divided in half by a wooden 10 barrier. A stock solution of the antidote was atomized directly onto the exposed seeds and soil in the open furrow on one side of the barrier. Ihe seeds in the entire flat were then covered with the previously removed soil. Ihe antidotally untreated sections of flats were compared for observed differences which would indicate lateral movement 15 of the antidote through the soil.

Control flats contained crops treated with herbicide only. All flats were placed on greenhouse benches where temperature was maintained between 70 and 90°F (21.1 to 32.2°C). dhe flats were watered by sprinkling as needed to assure good plant growth.

All of the soil used in the tests described herein was loamy sand soil treated with 50 parts per million (ppm) each of a comnerci-ally available fungicide, N-[ (trlchloromethyl)-thio]-4-cyclohexene-l, 2-dicarboxjjnide, and 18-18-18 fertilizer, which contains 18? by weight equivalent each of nitrogen, phosphorus pentoxide, and potassium oxide. ^ r\t n r " - . ' ■ ' ; y d7 Injury ratings were taken four weeks after application of the antidote. The effectiveness of the antidote was determined by visual comparison of crop injury in the test flats to that in the control flats.

Ihe treated crops initially screened for diminution of herbi cidal injury were milo, wheat, rice, barley, corn and soybeans. Can-pounds which showed substantial activity were tested further. Ihe herbicides and the most active antidote compositions were then screened on weed species. The weed species tested included watergrass 10 (Echinochloa crusgalll), foxtail (Setaria viridis), wild oat (Avena fatua), shattercane (Sorghum bicolor), johnsongrass (Sorghum halepense) and mustard (Brassllca juncea).

KEY TO TABLES IV AND V Compound numbers in these tables correspond to the numbers and their chemical description in Table I. Compounds omitted in Table 15 V were not tested on weed species.

Herbicides VERNAM® - S-propyl N,N-dipropyl thiocarbamate EPTAM® - S-ethyl N,N-dipropyl thiocarbamate RONEET® - S-ethyl N-ethyl-N-cyclohexyl thiocarbamate SUTAN® - S-ethyl N,N-diisobutyl thiocarbamate LASSO® - 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide TERIDOX® - 2-chloro-2*,6'-dimethyl-N-(methoxyethyl) acetanilide ^(-trif luoro-2,6-dinitro-N,N-dipropyl-f>-toluidine TREFLAN® ATRAZINE® - 2-chloro-4-ethylamino-6-isopropylamino-S-triazine Application Methods PES = Surface application of herbicide to soil after planting of seeds and prior to emergence of plants.

IF = In-furrow surface application of antidote (soil previously treated with herbicide only). 16 PPI = Pre-plant incorporation of herbicide or antidote. If both herbicide and antidote were preplant incorporated, a tank-mixed solution was used.

TM = Tank-mixed solution of herbicide and antidote.

If no antidote was applied, the word "none" appears in the Antidote Rate column. Ihe results shown on this line are the percent injuries sustained by each of the crops when treated with the herbicide only at the rate specified.

All rates shown, for both herbicide and antidote, are in pounds per acre.

Injury Ratings Ihe injury to the crop (Table IV) or weeds (Table V) is shown as a percentage.of damage done to the plants as compared to an evaluation of the undamaged state of the plants. The damage done to 10 the plants is a function of the number of plants injured and the extent of injury to each plant. This rating is made four (4) weeks after application of the herbicide alone or of the herbicide in combination with the antidote.

An asterisk (*) in Table IV indicates that the antidote 15 compound is active in reducing herbicidal injury to the crop.

Parentheses around a number indicate that the test has been run more than once and the results are inconclusive.

Table V shows that the antidote compounds tested have no effect on weeds, i.e., herbicidal injury to the weeds is sustained even 20 in the presence of an antidote compound. o o • TABLE IV Antidotal Effectiveness Cmpd. Herbicide Antidote Antidote Milo Wheat No. Herbicide Rate Method Rate Method % Inj % Inj 1 VERNAM 1.0 PPI none - 100 77 VERNAM 1.0 PPI 5-0 IP 100 *60 VERNAM 6.0 PPI none — VERNAM 6.0 PPI -0 IP VERNAM 1.0 PPI none VERNAM 1.0 PPI 1.0 IP VERNAM 1.0 PPI .0 IF VERNAM 1.0 PPI none _ 100 VERNAM 1.0 - PPI 1.0 IP *70 VERNAM 1.0 PPI .0 IP *60 VERNAM 6.0 PPI none VERNAM 6.0 PPI/™ 1.0 PPI/IM VERNAM 6.0 PPI/IM .0 PPI/LM VERNAM 6.0 PPI none VERNAM 6.0 PPI/IM 1.0 PPI/IM VERNAM 6.0 PPI/M .0 PPI/IM EPIAM 6.0 PPI none EPTAM 6.0 PPI 0.5 PPI EFPAM 6.0 PPI .0 PPI LASSO 3.0 PES none 98 70 LASSO 3.0 PES .0 IF 98 70 LASSO 3.0 PES none 90 55 LASSO 3.0 PES/TM -0 PES/TM 90 *40 Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 50 87 83 50 87 *20 90 100 *20 *80 60 *30 *10 60 60 60 60 60 60 80 *70 150 O & o vO & < > o • • m • TABLE IV (continued) Cmpd.

Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn No.

Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj ■ % Inj 1 LASSO 4.0 PES none - 80 LASSO 4.0 PES/1M .0 PES/1M *20 TREFLAN 1.0 PPI none 100 98 100 85 TREFLAN 1.0 PPI .0 IF 100 98 100 85 2 VERNAM 1.0 PPI none 100 '75 70 95 70 VERNAM 1.0 PPI .0 IF *80 *60 70 95 *50 VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF VERNAM 6.0 PPI none 90 VERNAM 6.0 PPI .0 IF *50 VERNAM 1.25 PPI none 70 VERNAM 1.25 PPI 1.0 IF *40 VERNAM 1.25 PPI .0 IF *30 Soybean % In.1 80 80 co vernam 1.25 ppi none - 70 vernam 1.25 ppi/im 1.0 ppi/im *50 vernam 1.25 ppi/im .0 ppi/im *35 lasso 3-5 pes none _ 95 70 100 70 lasso 3-5 pes .0 if *60 70 100 *50 teridox 1.0 pes none 100 70 80 100 teridox 1.0 pes .0 if 100 70 *55 100 3 VERNAM 1.0 ppi none - 95 70 70 95 50 VERNAM 1.0 ppi .0 if 95 *30 80 95 * 0 VERNAM 6.0 ppi none 70 55 VERNAM 6.0 ppi .0 if *30 *40 © o Cmpd. No. - 2 J U L1985 mj jger^si Herbicide Rate VERNAM 1.25 VERNAM 1.25 VERNAM 1.25 IP PPI PPI PPI none 1.0 .0 TABLE IV (continued) Herbicide Antidote Method Rate Antidote Method IP IP Milo % In.j Wheat * InJ 95 95 *60 VERNAM .0 PPI none - VERNAM .0 PPI 1.0 IP VERNAM .0 PPI .0 IP EPTAM 6.0 PPI none EPrAM 6.0 PPI 0.5 PPI EPTAM 6.0 PPI .0 PPI SUTAN .0 PPI none — SUTAN .0 PPI/IM 1.0 PPI/IM SUTAN .0 PPI/TM .0 PPI/IM LASSO 3.0 PES none — 90 55 LASSO 3.0 PES/TM .0 PES/IM *80 *35 LASSO 4.0 PES none _ LASSO 4.0 PES/IM .0 PES/IM VEHNAM— —1.05 —PPi none VERNAM 1.25 PPI .0 VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 VERNAM 1^25. "none VERNAM-— JL • C.J PPI 1.0 1.20 —PPi 5r6- IP IP IP * -aee- *40 *60 • # • Cotton Rice Barley Corn % In.1 % Inj % Inj % Inj 95 80 95 *60 95 *40 Soybean % Inj 35 *20 80 *20 40 40 *30 80 *10 *30 vo 6o 95 *20 i» o TABLE IV (continued) Cmpd.

No. vHerbicide Rate 3F Herbicide Antidote WIMAM 1.05 "VERNAM 1.25 VERNAM 1.25 VERNAM 1.25.

EPTAM 6.0 EPTAM 6.0 EPTAM 6.0 RONEET 3.0 RONEET 3.0 RONEET 3.0 LASSO 3.0 LASSO 3.0 LASSO 3.5 LASSO 3.5 TERIDOX 1.0 TERIDOX 1.0 ATRAZINE 1.0 ATRAZINE 1.0 ATRAZINE ATRAZINE ^tf.25 VERNAM VERNAM Method -PPI— PPI/TM PPI/IM PPI/IM PPI PPI PPI PPI PPI PPI PES PES PES PES 1.25 1.25 PPI PPI Rate none 0.25 0.5 1.0 none 0.5 .0 Antidote Method PPI/TM PPI/IM PPI/IM PPI PPI Milo Wheat % Inj % Inj none 5.0 none 5.0 IP 100 *75 100 *90 80 * 0 * 0 99 99 100 70 100 *15 80 100 *35 * 0 70 100 70 100 100 100 100 85 100 85 60 100 90 *50 *90 *70 50 O o (I > o • TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Milo Wheat No. Herbicide Rate Method Rate Method % Inj % Inj VERNAM 6.0 PPI none VERNAM 6.0 PPI 5.0 IP VERNAM 1.0 PPI none 100 77 VERNAM 1.0 PPI .0 IF- *60 *60 VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF VERNAM 1.0 PPI none 100 VERNAM 1.0 PPI 1.0 IP 100 VERNAM 1.0 PPI .0 IP 100 VERNAM 6.0 PPI none VERNAM 6.0 P^I/TM 1.0 PPI/IM VERNAM 6.0 PPI/TM 2.0 PPI/IM VERNAM 6.0 PPI/IM .0 PPI/IM VERNAM 6.0 PPI none VERNAM 6.0 PPI/IM 1.0 PPI/IM VERNAM 6.0 PPI/IM .0 PPI/IM VERNAM 6.0 PPI none __ VERNAM 6.0 PPI/IM 1.0 PPI/IM VERNAM 6.0 PPI/IM .0 PPI/IM EPTAM 6.0 PPI none — EPTAM 6.0 PPI 0.5 PPI EPTAM 6.0 PPI .0 PPI LASSO 3.0 PES none 98 70 LASSO 3.0 PES .0 IP 98 70 Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 95 50 *70 60 50 87 83 50 87 *60 90 60 * 0 90 60 *(45) *50 ru 60 M 60 (60) 60 60 *( 0) 60 *30 80 •30 « 0 99 o 99 O vO XI o o • TABLE IV (continued) Cmpd. Herbicide Antidote Antidote Mllo Wheat No. Herbicide Rate Method Rate Method % Inj % Inj 6 ATRAZINE 0.25 PES none ATRAZINE 0.25 PES 5.0 IF ATRAZINE 1.0 PES none - 100 ATRAZINE 1.0 PES .0 IF 100 TREFLAN 1.0 PPI none _ 100 98 TREFLAN 1.0 PPI -0 IF 100 *95 VERNAM 1.0 PPI none 100 77 VERNAM 1.0 PPI .0 IF 100 77 VERNAM 6.0 PPI none _ VERNAM 6.0 PPI .0 IF VERNAM 6.0 PPI none VERNAM 6.0 PPI/IM 1.0 PPI/TM VERNAM 6.0 PPI/IM .0 PPI/TM VERNAM 1.0 PPI none - VERNAM 1.0 PPI .0 IF VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF VERNAM 1.25 PPI none _ VERNAM 1.25 PPI 1.0 IF VERNAM 1.25 PPI .0 IF VERNAM 6.0 PPI none VERNAM 6.0 PPI/TM 1.0 PPI/IM VERNAM 6.0 .

PPI/TM .0 PPI/TM Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 70 100 70 100 100 85 100 *80 50 87 83 *40 87 83 70 95 70 70 95 *20 90 * 0 70 70 70 100 100 90 60 *40 90 60 R5 60 75 80 100 60 60 60 o O TABLE IV (continued) Wheat % Inj Cmpd.

Herbicide Antidote Antidote Milo No.

Herbicide Rate Method Rate Method % Inj 8 EPTAM 6.0 PPI none — EPTAM 6.0 PPI 0.5 PPI EPTAM 6.0 PPI .0 PPI RONEET 4.0 PPI none — 60 RONEET 4.0 PPI 1.0 IP 60 RONEET 4.0 PPI .0 IF *20 LASSO 3.0 PES none _ 98 70 LASSO 3.0 PES .0 IF 98 70 LASSO 3.5 PES none _ 95 70 LASSO 3.5 PES .0 IP 95 *60 TERIDOX 1.0 PES none 100 70 TERIDOX 1.0 PES -0 IP 100 70 ATRAZINE 0.25 PES none _ ATRAZINE 0.25 PES .0 IF ATRAZINE 1.0 PES none 100 ATRAZINE 1.0 PES .0 IF 100 TREFLAN 1.0 PPI none _ 100 98 TREFLAN 1.0 PPI .0 IF 100 98 VERNAM 1.0 PPI none 100 75 VERNAM 1.0 PPI .0 IF *90 75 VERNAM 6.0 PPI none — VERNAM 6.0 PPI .0 IF Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 80 *30 * 0 99 99 100 100 70 70 70 70 100 100 100 100 95 *50 70 70 80 80 100 100 ro uo 100 100 98 98 70 *60 80 95 M e # » • TABLE IV (continued) Cmpd.

Herbicide Antidote Antidote No.

Herbicide Rate Method Rate Method 9 VERNAM VERNAM 6.0 6.0 PPI PPI none 5.0 IF VERNAM VERNAM VERNAM 6.0 6.0 6.0 PPI PPIAM PPI/IM none 1.0 .0 PPI/IM PPI/TM VERNAM VERNAM 6.0 6.0 PPI PPI/TM none 5.0 PPI/TM Milo % Inj Wheat % In,1 EPTAM 6.0 PPI none — EPTAM 6.0 PPI 0.5 PPI EPTAM 6.0 PPI .0 PPI VERNAM 1.25 PPI none VERNAM 1.25 PPI .0 IF VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF VERNAM .0 PPI none _ VERNAM .0 PPI 1.0 IF VERNAM .0 PPI .0 IF 80 *30 80 *60 EPTAM 6.0 PPI none — EPTAM 6.0 PPI/TM 0.05 PPI/TM EPTAM 6.0 PPI/TM 0.5 PPI/TM EPTAM 6.0 PPI/TM .0 PPI/TM EPTAM 6.0 PPI none EPTAM 6.0 PPI/TM 0.5 PPI/TM EPTAM 6.0 PPI/TM . .0 PPI/IM Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 90 * 0 60 60 60 80 *70 *45 70 95 70 *50 95 *50 90 *30 *20 60 80 ro x= 90 50 * 0 *30 65 *50 80 90 90 90 to *35 o Cmpd.

No. 11 12 • O • 1 TABLE IV (continued) Herbicide Antidote Antidote Milo Wheat Herbicide Rate Method Rate Method % Inj % Inj RONEET 4.0 PPI none — 60 RONEET 4.0 PPI 1.0 IP 60 RONEET 4.0 PPI .0 IP 60 VERNAM 1.25 PPI none 80 80 VERNAM 1.25 PPI .0 IP *40 *60 VERNAM 6.0 PPI none ♦ VERNAM 6.0 PPI .0 IP EPTAM 6.0 PPI none EPTAM 6.0 PPI/IM 0.05 PPI/TM EPTAM 6.0 PPI/IM 0.5 PPI/IM EPTAM 6.0 PPI/IM .0 PPI/TM EPTAM 6.0 PPI none EPTAM 6.0 PPI/TM 0.5 PPI/TM EPTAM 6.0 PPI/TM .0 PPI/IM RONEET 4.0 PPI none 60 RONEET 4.0 PPI 60 RONEET 4.0 PPI *40 VERNAM 1.25 PPI none 100 95 VERNAM 1.25 PPI .0 IP *60 *6o VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF EPTAM 6.0 PPI none EPTAM 6.0 PPI/TM 0.05 PPI/TM EPTAM 6.0 PPI/TM 0.5 PPI/TM EPTAM 6.0 PPI/TM .0 PPI/TM Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 70 95 70 70 95 *50 60 100 90 60 100 *60 90 50 * 0 70 90 90 (90) *80 90 *(55) *25 ro VJl M 85 70 * 0 70 90 90 *80 * 0 S| o* • # • • • • TABLE IV (continued) Cmpd.

Herbicide Antidote Antidote Milo Wheat Cotton Rice Barley Corn Soybean No.

Herbicide Rate Method Rate Method % Inj % Inj % Inj % Inj % Inj % Inj % Inj 12 EPTAM 6.0 PPI none — 90 EPTAM 6.0 PPIAM 0.5 PPI/TM *40 EPTAM 6.0 PPI/TM .0 PPI/TM *10 EPTAM 6.0 PPI none 70 EPTAM 6.0 PPI 0.5 PPI *40 EPTAM 6.0 PPI .0 PPI * 0 13 VERNAM 1.25 PPI none 100 90 60 95 85 VERNAM 1.25 PPI .0 IF 100 90 60 95 85 VERNAM 6.0 PPI none 90 65 VERNAM 6.0 PPI .0 IF *65 70 14 VERNAM 1.25 PPI none 100 95 70 100 95 VERNAM 1.25 PPI .0 IF 100 95 *55 100 95 VERNAM 6.0 PPI none 90 65 VERNAM 6.0 PPI .0 IF *80 *40 VERNAM 1.25 PPI none — 100 95 70 100 95 VERNAM 1.25 PPI .0 IF 100 • 95 *40 100 *80 VERNAM 6.0 PPI none 90 65 VERNAM 6.0 PPI .0 IF *80 65 VERNAM 1.25 PPI none 50 VERNAM 1.25 PPI 1.0 IF 50 VERNAM 1.25 PPI .0 IF *20 16 VERNAM 1.25 PPI none 100 95 70 100 95 VERNAM 1.25 PPI .0 IF 100 95 70 100 100 TABLE IV (continued) Cmpd.

No. 16 Herbicide Antidote Antidote 17 18 Herbicide Rate Method Rate Method VERNAM 6.0 PPI none - VERNAM 6.0 PPI .0 IP EPTAM -0 PPI none EPTAM .0 PPIAM 0.05 PPI/TM EPTAM .0 PPIAM 0.5 PPI/TM EPTAM .0 PPIAM .0 PPI/IM VERNAM 1.25 PPI none _ VERNAM 1.25 PPI .0 IP VERNAM 6.0 PPI none _ VERNAM 6.0 PPI .0 IF VERNAM 1.25 PPI none _ VERNAM 1.25 PPI .0 IP VERNAM 6.0 PPI none _ VERNAM 6.0 PPI .0 IF VERNAM 1.0 PPI none — VERNAM 1.0 PPI 1.0 IF VERNAM 1.0 PPI .0 IF VERNAM 1.25 PPI none — VERNAM 1.25 PPI 1.0 IP VERNAM 1.25 PPI .0 IF EPTAM 6.0 PPI none — EPTAM 6.0 PPIAM 0.05 PPI/TM EPTAM 6.0 PPIAM 0.5 PPI/TM EPTAM 6.0 PPIAM .0 PPIAM EPTAM 6.0 PPI none — EPTAM 6.0 PPI/IM 0.5 PPI/IM EPTAM 6.0 PPIAM -0 PPI/TM Milo % Inj Wheat j Inj Cotton % Inj Rice % Inj Barley % Inj 100 *80 100 *95 60 60 100 100 90 *80 75 *60 55 55 90 *50 98 *60 *20 90 *80 60 *i*5 85 85 85 Corn % Inj 90 *30 85 *60 * 0 * 0 95 *85 90 *30 90 90 *80 * 0 90 *50 * 0 Soybean % Inj —mr~ *50 60 60 ro 60 60 M • # t TABLE IV (continued) Cmpd. No. 19 Herbicide Antidote Antidote Milo 21 Herbicide Rate Method Rate Method % Inj VERNAM 1.25 PPI none _ 100 VERNAM 1.25 PPI .0 IP *80 VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IP VERNAM 6.0 PPI none VERNAM 6.0 PPI 1.0 IP VERNAM 6.0 PPI .0 IP VERNAM 1.25 PPI none _ 100 VERNAM 1.25 PPI .0 IF 100 VERNAM 6.0 PPI none __ VERNAM 6.0 PPI .0 IF EPTAM .0 PPI none —.

EPTAM .0 PPI/IM 0.05 PPI/TM EPTAM -0 PPI/TM 0.5 PPI/IM EPTAM .0 PPI/IM .0 PPI/TM EPTAM 6.0 PPI none EPTAM 6.0 PPI/TM 0.05 PPI/TM EPTAM 6.0 PPI/TM 0.5 PPI/TM EPTAM 6.0 PPI/TM .0 PPI/TM VERNAM 1.25 PPI none 80 VERNAM 1.25 PPI -0 IF 80 VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IF Wheat % Inj 100 *95 100 100 75 75 Cotton Rice Barley Corn Soybean % In,j % Inj % Inj % Inj % Inj 60 100 90 70 100 90 60 100 90 60 *95 90 60 85 65 60 *65 *60 95 60 *60 *40 55 55 *45 95 60 *40 60 85 85 *35 *15 90 90 90 *30 90 60 *60 60 ro oo O N & TABLE IV (continued) Cmpd.

No. 21 Herbicide Antidote Antidote 22 Herbicide Rate Method Rate Method VERNAM 1.25 PPI none — VERNAM 1.25 PPI 1.0 IP VERNAM 1.25 PPI .0 IP VERNAM 6.0 PPI none __ VERNAM 6.0 PPI 1.0 IP VERNAM 6.0 PPI .0 IP VERNAM 6.0 PPI none VERNAM 6.0 PPI/IM 1.0 PPI/IM VERNAM 6.0 PPI/IM 2.0 PPI/IM VERNAM 6.0 PPI/TM .0 PPI/IM SUTAN 6.0 PPI none __ SUTAN 6.0 PPI/TM 1.0 PPI/TM SUTAN 6.0 PPI/TM .0 PPI.TM VERNAM 1.25 PPI none VERNAM 1.25 PPI .0 IP VERNAM 6.0 PPI none VERNAM 6.0 PPI .0 IP Milo Wheat % In.1 90 *60 100 100 Cotton Rice Barley Corn Soybean % Inj % Inj % Inj % Inj % Inj 50 50 50 *10 25 40 40 40 70 100 75 70 100 75 50 50 50 50 90 40 90 40 ro KO to O © sO VI O* I # • TABLE V Herbicidal Effectiveness Cmpd.

Herbicide Antidote Antidote Water No.

Herbicide Rate Method Rate Method grass 1 VERNAM 1.0 PPI none - 70 VERNAM 1.0 PPI 1.0 IP 70 VERNAM 1.0 PPI .0 IP 70 VERNAM 1.0 PPI none 100 VERNAM 1.0 PPI 1.0 IP 100 VERNAM 1.0 PPI .0 IP 100 VERNAM 6.0 PPI none — 100 100 VERNAM 6.0 PPI/IM 1.0 PPI/TM 100. 100 VERNAM 6.0 PPI/IM .0 PPI/TM 100 100 VERNAM 6.0 PPI none — 85 90 VERNAM 6.0 PPI/TM 1.0 PPI/IM 85 90 VERNAM 6.0 PPI/TM .0 PPI/TM 85 90 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 LASSO 3.0 PES none 99 LASSO 3.0 PES .0 IP 99 LASSO 3.0 PES none 100 100 LASSO. 3.0 PES/TM .0 PES/TM 100 100 LASSO 4.0 PES none 100 100 LASSO 4.0 PES/TM .0 PES/TM 100 100 > Shatter- Johnson Wild Oat cane Mustard grass 95 95 95 70 70 70 OJ o fO o © **0 xj 0^ TABLE V (continued) Herbicide Antidote Antidote Water Herbicide Rate Method Rate Method grass Foxtail VERNAM 1.25 PPI none 90 VERNAM 1.25 PPI 1.0 IP 90 VERNAM 1.25 PPI .0 IP 90 VERNAM 1.25 PPI none 85 VERNAM 1.25 PPI/IM 1.0 PPI/IM 85 VERNAM 1.25 PPI/IM .0 PPI/TM 85 LASSO 3.5 PES none 100 LASSO 3.5 PES .0 IP 100 TERIDOX 1.0 PES none 100 TERIDOX 1.0 >PES .0 IF 100 VERNAM 1.25 PPI none 85 VERNAM 1.25 PPI 1.0 IP 85 VERNAM 1.25 PPI .0 IP 85 VERNAM -0 PPI none 100 100 VERNAM .0 PPI 1.0 IF 100 100 VERNAM .0 PPI .0 ■ IP 100 100 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 Shatter- Johnson Wild Oat cane Mustard grass 100 100 100 100 100 100 uo O © TABLE V (continued) Cmpd.

Herbicide Antidote Antidote Water No.

Herbicide Rate Method Rate Method grass Foxtail 3 SUTAN .0 PPI none 100 SUTAN .0 PPI/TM 1.0 PPI/TM 100 SUTAN .0 PPI/TM .0 PPI/IM 100 LASSO 3.0 PES none 100 100 LASSO 3-0 PES/IM .0 PES/IM 100 100 LASSO 4.0 PES none 100 100 LASSO 4.0 PES/TM .0 PES/TM 100 100 4 VERNAM 1.25 PPI none 100 VERNAM 1.25 PPI 1.0 IP 100 VERNAM 1.25 PPI .0 IP 100 VERNAM 1.25 PPI none 70 VERNAM 1.25 PPI/IM 0.25 PPI/TM I 70 VERNAM 1.25 PPI/IM 0.5 PPI/TM 70 VERNAM 1.25 PPI/TM 1.0 PPI/TM 70 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 RONEET 3.0 PPI none 95 RONEET 3.0 PPI 1.0 IF 95 RONEET 3.0 PPI .0 IP 95 Shatter- Johnson Wild Oat cane Mustard grass 100 100 100 70 70 70 100 ft 100 100 100 100 100 r * 100 gSJ o \D OS TABLE V (continued) Herbicide Antidote Antidote Water Herbicide Rate Method Rate Method grass Foxtail LASSO 3-0 PES none 99 LASSO 3-0 PES .0 IP 99 LASSO 3-5 PES none 100 LASSO 3.5 PES .0 IP 100 TERIDOX 1.0 PES none 100 TERIDOX 1.0 PES .0 IF 100 ATRAZINE 0.25 PES none _ 95 ATRAZINE 0.25 PES .0 IF 95 VERNAM 1.0 PPI none 70 VERNAM 1.0 PPI 1.0 IF 70 VERNAM 1.0 PPI .0 IP 70 VERNAM 6.0 PPI none 100 90 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 90 VERNAM 6.0 PPI/IM 2.0 PPI/IM 100 90 VERNAM 6.0 PPI/IM .0 PPI/TM 100 90 VERNAM 6.0 PPI none 100 100 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 100 VERNAM 6.0 PPI/TM .0 PPI/TM 100 100 VERNAM 6.0 PPI none _ 85 90 VERNAM 6.0 PPI/IM 1.0 PPI/IM 85 90 VERNAM 6.0 PPI/TM .0 PPI/TM 85 90 Shatter- Johnson Wild Oat cane Mustard grass 100 100 100 100 100 OJ O o TABLE V (continued) Cmpd.

Herbicide Antidote Antidote Water No.

Herbicide Rate Method Rate Method grass Foxtail 6 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 LASSO 3.0 PES none _ 99 LASSO 3.0 PES .0 IP 99 ATRAZINE 0.25 PES none 95 ATRAZINE 0.25 PES .0 IP 95 7 VERNAM 6.0 PPI none 85 90 VERNAM 6.0 PPI/IM 1.0 PPI/TM 85 90 VERNAM 6.0 PPI/IM .0 PPI/3M 85 90 8 VERNAM 1.25 PPI none — 90 VERNAM 1.25 PPI 1.0 IP 90 VERNAM 1.25 PPI .0 IP 90 VERNAM 6.0 PPI none 100 100 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 100 VERNAM 6.0 PPI/TM .0 PPI/TM 100 100 EPTAM 6.0 PPI none 100 100 eptam 6.0 PPI 0.5 . PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 RONEET 4.0 PPI none — 80 RONEET 4.0 PPI 1.0 IF 80 RONEET 4.0 PPI .0 IP 80 Shatter- Johnson Wild Oat cane Mustard grass 100 100 100 -fc- © s© TABLE V (continued) Cmpd. No.

Herbicide Rate Herbicide Method Antidote Rate Antidote Method Water grass Foxtail 8 LASSO 3.0 PES none 99 LASSO 3.0 PES .0 IP 99 LASSO 3.5 PES none 100 LASSO 3.5 PES .0 IF 100 TERIDOX 1.0 PES none — 100 TERIDOX 1.0 PES .0 IF 100 ATRAZINE 0.25 PES none 95 ATRAZINE 0.25 PES .0 IF 95 9 VERNAM 6.0 PPI none 100 100 VERNAM 6.0 PPI/TM 1.0 PPI/TM 100 100 VERNAM 6.0 PPI/TM .0 PPI/TM 100 100 VERNAM 6.0 PPI none 85 90 VERNAM 6.0 PPI/TM .0 PPI/TM 85 90 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI 0.5 PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 VERNAM .0 PPI none 100 95 VERNAM .0 PPI 1.0 IF 100 95 VERNAM .0 PPI .0 IF 100 95 Shatter*- Johnson Wild Oat cane Mustard grass 100 100 uo *J1 O o xi o TABLE V (continued) Herbicide Antidote Antidote Water Herbicide Rate Method Rate Method grass Foxtail EPTAM 6.0 PPI none 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 EPTAM 6.0 PPI/TM .0 PPI/IM 100 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI/IM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM .0 PPI/TM 100 100 RONEET 4.0 PPI none 80 RONEET 4.0 PPI 1.0 IP 80 RONEET 4.0 PPI .0 IP 80 EPTAM 6.0 fcPI none 100 EPTAM 6.0 PPI/TM 0.05 PPI/TM 100 EPTAM 6.0 PPI/TM 0.5 PPI/IM 100 EPTAM 6.0 PPI/TM • 5.0 PPI/TM 100 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI/IM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/TM .0 PPI/TM 100 100 RONEET 4.0 PPI none — 80 RONEET 4.0 PPI 80 RONEET 4.0 PPI 80 EPTAM 6.0 PPI none 100 EPTAM 6.0 PPI/TM 0.05 PPI/IM 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM- 100 EPTAM 6.0 PPI/TM -0 PPI/TM 100 Shatter*- Johnson Wild Oat cane Mustard grass 100 100 100 100 100 100 100 100 100 & 100 100 100 ° K «\ ioo N-* 100 G> 100 100 100 *jni TABLE V (continued) Cmpd. No.

Herbicide Rate Herbicide Method Antidote Rate Antidote Method Water grass Foxtail 12 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI/IM 0.5 PPI/TM 100 100 EPTAM 6.0 PPI/IM .0 PPI/IM 100 100 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPI . 0.5 PPI 100 100 EPTAM 6.0 PPI .0 PPI 100 100 VERNAM 1.25 PPI none 90 70 VERNAM 1.25 PPI 1.0 IP 90 70 VERNAM 1.25 PPI .0 IP 90 50 16 EPTAM .0 PPI none 98 EPTAM -0 Pi>I/TM 0.05 PPI/TM 98 EPTAM .0 PPI/IM 0.5.

PPI/TM 98 EPTAM .0 PPI/IM .0 PPI/TM 98 18 VERNAM 1.0 PPI none 97 85 VERNAM 1.0 PPI 1.0 IP 97 85 VERNAM 1.0 PPI .0 IF 97 85 VERNAM 1.25 PPI none 90 85 VERNAM 1.25 PPI 1.0 IF 90 85 VERNAM 1.25 PPI .0 IP 90 85 EPTAM 6.0 PPI none 100 EPTAM 6.0 PPI/IM 0.05 PPI/TM 100 EPTAM 6.0 PPI/TM 0.5 PPI/TM 100 EPTAM 6.0 PPI/IM .0 PPI/TM 100 Shatter^ Johnson Wild Oat cane Mustard grass 98 98 98 98 ioo JO 100 100 O ioo TABLE V (continued) Cmpd.

Herbicide Antidote Antidote Water No.

Herbicide Rate Method Rate Method grass Foxtail 18 EPTAM 6.0 PPI none 100 100 EPTAM 6.0 PPIAM 0.5 PPIAM 100 100 EPTAM 6.0 PPIAM .0 PPI/IM 100 100 19 VERNAM 6.0 PPI none. _ 100 100 VERNAM 6.0 PPI 1.0 IP 100 100 VERNAM 6.0 PPI .0 IP 100 100 EPTAM -0 PPI none 98 EPTAM .0 PPIAM 0.05 PPI/TM 98 EPTAM .0 PPIAM 0.5 PPI/TM 98 EPTAM .0 PPIAM -0 PPI/TM 98 EPTAM 6.0 PPI none _ 100 EPTAM 6.0 PPIAM 0.05 PPI/IM 100 EPTAM 6.0 PPIAM 0.5 PPI/TM 100 EPTAM 6.0 PPIAM .0 PPI/TM 100 21 VERNAM 1.25 PPI none _ 95 80 VERNAM 1.25 PPI 1.0 IP 95 80 VERNAM 1.25 PPI .0 IP 95 80 VERNAM 6.0 PPI none 95 95 VERNAM 6.0 PPI 1.0 IP 95 95 VERNAM 6.0 PPI .0 IP 95 95 VERNAM 6.0 PPI none _ 100 97 VERNAM 6.0 PPIAM 1.0 PPI/TM 100 97 VERNAM 6.0 PPIAM 2.0 PPI/TM 100 97 VERNAM 6.0 PPIAM .0 PPI/TM 100 97 Shatter- Johnson Wild Oat cane Mustard grass 98 98 98 98 100 100 100 °° 100 ND O o sO a* Cmpd.

No. Herbicide Rate 21 SUTAN 6.0 PPI none SUTAN 6.0 PPIAM 1.0 SUTAN 6.0 PPI/IM 5.0 TABLE V (continued) Herbicide Antidote Method Rate Antidote Method PPI/TM PPI.TM Water grass 95 95 95 Poxtall Wild Oat 99 99 99 Shatter- cane Mustard Johnson grass LO MD I IM © O vo ■"s4 200976 40 Test Results The compounds of this invention show good antidotal activity for a variety of crops. Ihe composition of thiocarbamate herbicide and antidote compound was particularly effective for the reduction of herbicidal injury to com crops. Use of the antidote compounds did not 5 result in a reduction of herbicidal injury to weeds.

Formulations A formulation is the Incorporation of a formulant in a form which is directly usable on crops and weeds. As defined herein, a "formulant" is the material which is to be formulated. Ihe formulant may be either an antidote compound alone or an herbicide and antidote 10 composition. The purpose of the formulation is to apply the formulant to the locus where it is desired to establish herbicidal selectivity by a convenient method. The "locus" may include soil, seeds, seedlings and vegetation.

Ihe formulations are corrmonly dusts, wettable powders, gran-15 ules, solutions or emulsifiable concentrates.

Dusts are free-flowing powder compositions containing the formulant impregnated on a particulate carrier. The particle size of the carriers is usually in the approximate range of 30 to 50 microns. Examples of suitable carriers are talc, bentonite, dlatomaceous earth, 20 and pyrophyllite. The composition generally contains up to 50% of formulant. Anti-caking and anti-static agents may also be added.

EXists may be applied by spraying from boom and hand sprayers on airplanes .

Wettable powders are'finely divided compositions comprising a 25 particulate carrier impregnated with the formulant and additionally containing one or more surface active agents. The surface active agent promotes rapid dispersion of the powder In an aqueous medium to fonn stable, sprayable suspensions. A wide variety of surface active agents can be used, for example, long chain fatty alcohols and alkali metal 30 salts of the sulfated fatty alcohols; salts of sulfonic acid; esters of long chain fatty acids; and polyhydric alcohols, in which the alcohol groups are free, omegasubstituted polyethylene glycols of relatively 2 00976 41 long chain length. A list of surface active agents suitable for use in agriculture formulations can be found in Wade Van Valkenburg, Pesticide Formulations (Marcel Dekker, Inc., N.Y., 1973) at pages 79-84.

Granules comprise the formulant impregnated on a particulate 5 inert carrier having a particle size of about 1 to 2 millimeters (mm) in diameter. The granules can be made by spraying a solution of the formulant in a volatile solvent onto the granular carrier. Examples of suitable carriers for the preparation of granules include clay, vermiculite, sawdust, and granular carbon.

Qnulsifiable concentrates consist of an oil solution of the fonnulant plus an emulsifying agent. Prior to use the concentrate is diluted with water to form a suspended emulsion of oil droplets. The emulsifiers used are usually a mixture of anionic and nonionic surfactants. Other additives, such as suspending agents and thickeners, may 15 be included in the emulsiflable concentrate.

When the formulant is an antidote and herbicide composition, the proportion of antidote compound to herbicide compound generally ranges frcm approximately 0.001 to 30 parts by weight of the antidote compound per weight of the herbicide compound.

Formulations generally contain several additives in addition to the formulant and carrier or agent. Among these are inert ingredients, diluent carriers, organic solvents, water, oil and water, water In oil emulsions, carriers of dusts arid granules, and surface active wetting, dispersing and emulsifying agents. Fertilizers, e.g., aitmoni-25 urn nitrate, urea and superphosphate, may be included. Aids to rooting and growth, e.g., compost, manure, humus and sand, may also be included.

Alternatively, the antidote compounds and herbicide and antidote compositions of this invention can be applied to a crop by addi-30 tion of the formulant to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed.

Claims

200976 ' ■r.'ia.PV. * 42 As another alternative, the formulant can be applied to the soil in the form of a solution in a suitable solvent. Solvents frequently used in these formulations include kerosene, fuel oil, xylene, petroleum fractions with boiling ranges above xylene and aromatic petroleum fractions rich in methylated naphthalenes. Liquid solutions, like dusts, may be applied by spraying frcm bocm and hand sprayers on airplanes. WHAT CLAIM IS- 43 200976

1. A conpound having the formula 0 f-— O / Rt --tCX r3 )—0 r2 r/ in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; 5 R^ is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; 10 R3 is selected from the group consisting of hydrogen and lcwer alkyl having 1-4 carbon atons, inclusive; and R4 is hydrogen, provided that when R^, R2 and R4 are all hydrogen and r3 is hydrogen or lower alkyl having 1-4 carbon atons inclusive; then R is Other than a l-chloro-2-brcmo-ethy 1 or l-brono-2-chloro-ethyl radical. 15

2. A composition comprising a conpound as defined in Claim 1 formulated with an inert diluent carrier or agent.

3. A composition oonprising 20 (a) an herbicidally effective amount of a thiocarbamate com pound of the formula /J? * Rsv 0 A ^ *6 ^N-C-s-R7 in which 25 R5 is alkyl having 1-6 carbon atoms, inclusive; R5 is selected from the group consisting of alkyl having 1-6 carbon atoms, inclusive; and cyclohexyl; or ' ■ 200976 44 R5 and R$ form indistinguishable parts of a single alkylene ring having 4-10 carbon atoms, inclusive; and R7 is selected frcxn the group consisting of alkyl having 1-6 carbon atoms, inclusive? haloalkyl wherein halo is 5 selected from the group consisting of chlorine, bromine and iodine and alkyl has 1-6 carbon atoms, inclusive; alkenyl having 2-6 carbon atoms, inclusive; halo alkenyl wherein halo is selected from the group consisting of chlorine, bromine and iodine and alkenyl has 2-6 carbon 10 atcms, inclusive; benzyl; and halo-substituted benzyl, wherein halo is selected from the group oonsisting of chlorine, bromine and iodine; and (b) a non-phytotoxic antidotally effective amount of a conpound of the formula 15 in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atons, inclusive; Rl is selected from the group oonsisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon 20 atons, inclusive; and phenyl; R2 is selected from the group oonsisting of hydrogen and lower alkyl having 1-4 carton atoms, inclusive; R3 is selected from the group consisting of hydrogen and lcwer alkyl having 1-4 carbon atons, inclusive; 25 R4 is selected from the group oonsisting of hydrogen and a nitro phenyl group; and - either R3 is hydrogen or R4 is hydrogen, provided that when R-j_, R2 and R^ are all hydrogen and R3 is hydrogen or lower alkyl having 1-4 carbon atoms inclusive; then R is other than a l-chloro-2-brcno-ethyl or l-brcmo-2-chloro-ethyl radical. \ 30 200976 45

4. A ccnposition as defined in oithor of Claim 3 op 5- wherein R5, Rg and R7 are all propyl.

5. A composition as defined in eithep of Claim 3 op 5' wherein R5 and R$ are both propyl and R7 is ethyl. t 5

6. A conposition as defined in eifahci? of Claim 3 or-fr herein R5 and R7 are both ethyl and Rg is cyclohexyl.

7. A oonpositicn comprising: (a) an herbicidally effective amount of an acetanilide compound of the formula 10 in which R8 and R^q are independently selected from the group consisting of hydrogen; and alkyl having 1-6 carbon atons, inclusive; and Rg is selected from the group oonsisting of alkyl having 1-6 carboi atoms, inclusive; alkoxy having 1-8 carbon atoms, inclusive; 15 and carbethoxyalkyl wherein the alkyl group has 1-4 carboi atoms, inclusive; and (b) a ncn-phytotoxic antidotally effective amount of a conpound of the formula O .— 0 /Ri V R/)—O \R2 r4 in which 20 R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atons, inclusive; R} is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atons, inclusive; alkenyl having 2-4 car ben atons, inclusive; and phenyl; <'e N 7 *4. 201)1^85 P c J 300976 t 46 R2 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group oonsisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; 5 R4 is selected from the group consisting of hydrogen and a nitro phenyl group; and either R3 is hydrogen or R4 is hydrogen, provided that when R]_, R2 and R4 are all hydrogen and R3 is hydrogen or lower alkyl having 1-4 carbon atoms inclusive; then R is other than a l-chloro-2-brcmo-ethyl or l-brano-2-chloro-ethyl radical. 10 8. A ccnposition as defined in cithcr-o

8.S Claim 7 or wherein Rg and Rio are both ethyl and Rg is methoxymethyl.

9. A conposition as defined in cither of Claim 7 or 10' wherein Rg and R^q are both methyl and Rg is methoxyethyl.

10. A method of establishing herbicidal selectivity comprising 15 applying to the locus where selectivity is desired a non-phytotoxic antidotally effective amount of a conpound of the formula .jur1 ■ Ri >— 0 R2 ^ u • \\ ff\ Os fiu ui H- CD > i/ in. / R4 ach R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; 20 Ri is selected from the group consisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group oonsisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; 25 R3 is selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group oonsisting of hydrogen and a nitrophenyl group; and either R3 is hydrogen or R4 is hydrogen, provided that when r^, r2 and R4 are all hydrogen and r3 is hydrogen or lowar alkyl having 1-4 carbon atoms inclusive; then R is other than a 1—chloro-2—brcmo-ethyl or l-braro-2-chloro-ethyl radical. g-00976 47 i4*—A mefehod oa defined in Claim 13 ■ wherein R ia 1 ehloro 2— feromoy is hydrogen> Rg ia hydrogenf R3 io ethyl ond R4 io hydrogen.

11. A method of establishing herbicidal selectivity comprising applying to the locus where selectivity is desired a non-phytotoxic 5 antidotally effective amount of a conpositicn comprising: (a) an herbicidally effective amount of a thiocarbamate compound of the formula R5\ 0 °\ II N-C-S-R7 ^6 in which r5 is alkyl having 1-6 carbon atoms, inclusive; 10 R6 is selected from the group oonsisting of alkyl having 1-6 carbon atcms, inclusive; and cyclohexyl; or R5 and Rg form indistinguishable parts of a single alkylene ring having 4-10 carbon atoms, inclusive; and R7 is selected from the group consisting of alkyl having 1-6 15 carbon atoms, inclusive; haloalkyl wherein halo is selected from the group consisting of chlorine, bromine an^ iodine and alkyl has 1-6 carbon atoms, inclusive; //^ ac? alkenyl having 2-6 carbon atoms, inclusive; halo alkenyl j wherein halo is selected from the group consisting of chlorine, bromine and iodine and alkenyl has 2-6 carbon atoms, inclusive; benzyl; and halo-substituted benzyl, wherein halo is selected from the group consisting of chlorine, bromine and iodine; and (b) a non-phytotoxic antidotally effective amount of a compound 25 of the formula - 0 /—0 /Ri r^tCX r3 ^—0 r2 r4 in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; £00976 48 Rl is selected from the group oonsisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbon atoms, inclusive; and phenyl; R2 is selected from the group oonsisting of hydrogen and lower 5 alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group oonsisting of hydrogen and lower alkyl having 1-4 carbon atons, inclusive; r4 is selected from the group consisting of hydrogen and a nitro phenyl group; and 10 either R3 is hydrogen or R4 is hydrogen, provided that when R]_, R2 and R4 are all hydrogen and R3 is hydrogen or lower alkyl having 1-4 carbon atons inclusive; then R is other than a l-chloro-2-brono-ethyl or l-hrcmo-2-chloro-ethyl radical.

12. A method as defined in either of Claim H or 16 wherein R5, R6 and R7 are all propyl. 15

13. A method as defined in either of Claim 11 or 16 wherein r5 and Rg are both propyl and r7 is ethyl.

14. A method as defined in either of Claim 11 or 16 wherein R5 and R7 are both ethyl and Rg is cyclohexyl.

15. A method of establishing herbicidal selectivity comprising 20 applying to the locus where selectivity is desired a non-phytotoxic antidotally effective amount of a composition comprising: (a) an herbicidally effective amount of an acetanilide compound of the formula 25 in which Rg and Rio are independently selected from the group consisting of hydrogen; and alkyl having 1-6 carbon atoms, inclusive; and &.00976 R9 is selected from the group consisting of alkyl having 1-6 carbon atoms, inclusive; alkoxy having 1-8 carbon atoms, inclusive; and carbethoxyalkyl wherein the alkyl group has 1-4 carbon atoms, inclusive; and (b) a non-phytotoxic antidotally effective amount of a conpound of the formula 0 ,— OR-, R-C-NH_y \/ R^V—(AR2 r4 in which R is haloalkyl wherein halo is chlorine, bromine or iodine and the alkyl group has 1-4 carbon atoms, inclusive; R^ is selected from the group oonsisting of hydrogen; lower alkyl having 1-4 carbon atoms, inclusive; alkenyl having 2-4 carbcn atoms, inclusive; and phenyl; R2 is selected from the group oonsisting of hydrogen and lower alkyl having 1-4 carbon atoms, inclusive; R3 is selected from the group consisting of hydrogen and lcwer alkyl having 1-4 carbon atoms, inclusive; R4 is selected from the group oonsisting of hydrogen and a nitro phenyl group; and either R3 is hydrogen or R4 is hydrogen, provided that when %, R2 and R4 are all hydrogen and R3 is hydrogen or lower alkyl having • 1 4 carbon a turns inclusive; then R is other than a 1—chloro-2—hromo—ethyl or l-brono-2-chloro-ethyl radical.

16. A nethod as defined in Claim 15 wherein^ Rg and R^q are both ethyl and Rg is methoxymethyl. i \V _

17. A method as defined in Claim 15 wherein Rg and Rjq are both methyl and R9 is methoxyethyl.

18. Haloalkylcarbonylamino-1,3-dioxane herbicide antidotes substantially as specifically described herein in any one of the Examples.

19. A method of establishing herbicide selectivity which comprises applying to the locus where protection is desired an antidotally effective amount of a ccnpound according to Claim 1 substantially as specifically described herein in any one of t' " ' 'I 'M 50 the Examples. 200976 BALDWIN^ SON &£AE£Y ATTORNEYS FOR THE APPLICANTS